1. Field of the Invention
The present invention relates to polysulfonamide colorants which are useful as tints, toners, and colorants for a variety of applications where nonextractability of the colorant is important. Since the colorant moieties are incorporated into the polymer chain, the colorant is not leachable, sublimable or extractable and does not exude from the composition. The polysulfonamide colorants are useful in a wide variety of products such as plastics, fibers, films, cosmetics, skin creams or lotions, soaps, hair colorations, waxes, polishes, coatings, paints, toners for impactless printing, inks, and etc., which will be safe to humans since exposure to toxic dye molecules readily absorbed by the body is greatly minimized. Thus, the colorant compositions have utility in a wide variety of applications where toxicological concerns are evident. The colorants are particularly useful for imparting stable coloration to a wide variety of thermoplastic compositions including polyesters, polycarbonates, polyamides, cellulose esters, polyurethanes, polyolefins, etc. by conventional melt blending techniques.
Plastics, paints, printing inks, rubber, cosmetics, and similar materials are typically colored by organic pigments when superior brilliance and tinctorial strength are important. Toxicity considerations have presented chronic problems relative to the use of organic pigments since some have been shown to be potential carcinogens and to cause contact dermatitis.
Plastics are also colored by using color concentrates consisting of physical admixtures of polymers and colorants (usually solvent dyes). However, the use of such physical admixtures to color polymeric materials such as polyester, e.g., poly(ethylene terephthalate) and blends thereof, present a number of problems:
1. Colorant migration during drying of the colored polyester pellets. PA1 2. Colorant migration during extrusion and colorant accumulation on dies which can cause shutdowns for clean-up. Such colorant migration and accumulation result in time consuming and difficult clean-up, particularly when a polymer of another color is subsequently processed on the same equipment. PA1 3. Colorants may not mix well, for example, when using two or more color concentrates to obtain a particular shade. PA1 4. Colorants may diffuse or exude during storage and use of the colored polymeric material. PA1 X and X' are independently selected from the group consisting of Y, -Y-alkylene, -Y-(alkylene-Y'-).sub.m, -Y-alkylene-C.sub.3 -C.sub.8 -cycloalkylene, Y-C.sub.3 -C.sub.8 -cycloalkylene-Y', and Y-alkylene-C.sub.3 -C.sub.8 -cycloalkylene-alkylene-Y', wherein m is 1-3, and Y and Y' are independently --O--, --S--, --N(R)CO--, --N(R)SO.sub.2 --, or --N(R.sub.2)--; PA1 Ar and Ar' are independently a divalent benzene or naphthalene radical which may be substituted with from 1 to 4 substituents which may be the same or different and are selected from the group consisting of C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 alkoxy, C.sub.1 -C.sub.8 alkanolyamino, aroylamino, C.sub.1 -C.sub.8 alkylthio or halogen groups; PA1 R and R' are independantly hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.8 cycloalkyl, heteroaryl or aryl; PA1 R.sub.1 is a divalent organic radical, with the proviso that when R.sub.1 is ethylene, R and R' may be combined to represent an ethylene radical; PA1 R.sub.2 is selected from the group consisiting of hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.1 -C.sub.8 alkanoyl, aroyl, C.sub.1 -C.sub.8 alkylsulfonyl, arylsulfonyl, carbamoyl, or sulfamoyl; and n is an integer of from about 3 to about 30. PA1 a) two or more reactive dihalosulfonylanthraquinone intermediates are reacted with one or more diamines to give a colored polysulfonamide; PA1 b) two or more colored polysulfonamides are combined and then added to thermoplastic materials by known methods.
The polysulfonamide colorants eliminate or minimize the aforementioned problems associated with the use of conventional dyes and pigments.
2. Description of the Prior Art
It is known to produce polyester color concentrates having colorants copolymerized therein and to use these for coloring various materials including thermoplastics (See U.S. Pat. No. 5,032,670; U.S. Pat. No. 5,106,942; WO 92/07913; WO 92/13921). The polycondensation reactions required to prepare these polymeric colorants require high temperature conditions (&gt;250.degree. C.) and continuous large scale processing to be cost effective. This is in contrast to the polysulfonamide colorants of this invention which can be prepared at relatively low temperatures (e.g., usually 100.degree. C. or less) in batch processing equipment.
U.S. Pat. Nos. 2,994,693; 3,403,200; and 5,080,764 all disclose colored polysulfonamides. More particularly, U.S. Pat. No. 2,994,693 discloses polysulfonamides derived from colored diaminoanthraquinones and diacid halides such as diacid halides of carboxylic acids, bis-sulfonyl halides and bis-haloformates. In contrast to the colored polysulfonamides of our invention, which contain anthraquinone chromophores, the colors of the prior art polysulfonamides are greatly different from that of the starting diaminoanthraquinone monomers, thus making control of hue and shade difficult. In this invention, the colored anthraquinone monomer contains at least two sulfonyl halide groups which are isolated from the color producing system. Thus, no substantial shifts in color are experienced when the colored di-sulfonyl halides are reacted with the uncolored diamines.